Rapid Synthesis of γ-Arylated Carbonyls Enabled by the Merge of Copper- and Photocatalytic Radical Relay Alkylarylation of Alkenes

Lv, Xulu; Wang, Cong; Wang, Qiaoli; Shu, Wei

doi:10.1021/acs.orglett.8b03485

Cited by 68 publications

(31 citation statements)

References 60 publications

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“…Along these lines, protocols to access racemic products were first disclosed in 2012. The alkyl radicals are generated by reductive cleavage of alkyl halides, or by radical addition of N‐centered radicals, trifluoromethyl radicals, and alkyl radicals to alkenes, or by benzylic H abstraction using NFSI or peroxides …”

Section: Radical–metal Crossover Reactionsmentioning

confidence: 99%

“…Radical/Cu crossover reactions can also be applied to the cyanation or arylation of benzylic radicals using trimethylsilyl cyanide,c opper cyanide,ora ryl boronic acids as the cyanide and aryl donors.Along these lines,protocols to access racemic products were first disclosed in 2012. Thea lkyl radicals are generated by reductive cleavage of alkyl halides, [304] or by radical addition of N-centered radicals, [305] trifluoromethyl radicals, [306,307] and alkyl radicals [308,309] to alkenes,o rb y benzylic Habstraction using NFSI [310] or peroxides. [311] Recently,the group of Liu substantially contributed to the development of asymmetric variants of such transformations by using chiral bis(oxazoline) ligands.F or example,r adical alkene trifluoromethylation with concomitant b-cyanation [312] was accomplished with excellent enantioselectivity.I na nalogy,t rifluoromethylation and subsequent Cu-catalyzed stereoselective b-arylation [313] was reported (Figure 49 c).…”

Section: Reviewsmentioning

confidence: 99%

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The Persistent Radical Effect in Organic Synthesis

2019

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Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if the radicals have different lifetimes and if they are generated at equal rates, cross‐coupling will become the dominant process. This high cross‐selectivity is based on a kinetic phenomenon called the persistent radical effect (PRE). In this Review, an explanation of the PRE supported by simulations of simple model systems is provided. Radical stabilities are discussed within the context of their lifetimes, and various examples of PRE‐mediated radical–radical couplings in synthesis are summarized. It is shown that the PRE is not restricted to the coupling of a persistent with a transient radical. If one coupling partner is longer‐lived than the other transient radical, the PRE operates and high cross‐selectivity is achieved. This important point expands the scope of PRE‐mediated radical chemistry. The Review is divided into two parts, namely 1) the coupling of persistent or longer‐lived organic radicals and 2) “radical–metal crossover reactions”; here, metal‐centered radical species and more generally longer‐lived transition‐metal complexes that are able to react with radicals are discussed—a field that has flourished recently.

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Section: Radical–metal Crossover Reactionsmentioning

confidence: 99%

Section: Reviewsmentioning

confidence: 99%

The Persistent Radical Effect in Organic Synthesis

2019

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“…In diesem Zusammenhang wurden in 2012 Protokolle veröffentlicht, die den Zugang zu racemischen Produkten liefern. Die Alkyl‐Radikale werden durch die reduktive Spaltung von Alkylhalogeniden oder durch die radikalische Addition von N‐zentrierten, Trifluormethyl‐ und Alkyl‐Radikalen an Alkene oder durch benzylische H‐Abstraktion mit NFSI oder Peroxiden erzeugt …”

Section: Radikal‐metall‐kreuzungsreaktionenunclassified

“…In diesem Zusammenhang wurden in 2012 Proto-kolle verçffentlicht, die den Zugang zu racemischen Produkten liefern. Die Alkyl-Radikale werden durch die reduktive Spaltung von Alkylhalogeniden [304] oder durch die radikalische Addition von N-zentrierten, [305] Tr ifluormethyl- [306,307] und Alkyl-Radikalen [308,309] an Alkene oder durch benzylische H-Abstraktion mit NFSI [310] oder Peroxiden erzeugt. [311] Vork urzem trug die Gruppe von Liu erheblich zur Entwickelung einer asymmetrischen Va riante einer solchen Tr ansformation durch die Verwendung chiraler Bis(oxazolin)-Liganden bei.…”

Section: Kupferunclassified

Der “Persistent Radical Effect” in der organischen Chemie

2019

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Radikal‐Radikal‐Kupplungen sind nahezu diffusionskontrollierte Prozesse. Daher sind selektive Kreuzkupplungen zweier unterschiedlicher Radikale schwierig zu realisieren und stellen somit synthetisch nicht wertvolle Prozesse dar. Wenn die beiden Radikale allerdings eine unterschiedliche Lebensdauer aufweisen und in gleichen Raten gebildet werden, wird die Kreuzkupplung zum dominierenden Prozess. Die hohe Kreuzselektivität basiert auf einem kinetischen Phänomen, dem “Persistent Radical Effect” (PRE). In diesem Aufsatz wird eine von Simulationen einfacher Modellsysteme gestützte Erklärung des PRE geliefert. Weiter werden die Stabilität von Radikalen in Bezug auf ihre Lebensdauer und verschiedene Beispiele für PRE‐vermittelte Radikal‐Radikal‐Kupplungen in der Synthese diskutiert. Es wird gezeigt, dass der PRE nicht auf Kupplungen persistenter mit transienten Radikalen beschränkt ist. Der PRE mit einhergehender hoher Kreuzselektivität greift bereits, wenn ein Kupplungspartner langlebiger als das andere transiente Radikal ist. Diese Tatsache erweitert signifikant das Anwendungsgebiet PRE‐vermittelter Radikalchemie. Dieser Aufsatz ist in zwei Teile aufgeteilt: 1) die Kupplung persistenter oder langlebiger organischer Radikale und 2) Radikal‐Metall‐Kreuzungsreaktionen; hierbei werden Metall‐zentrierte Radikalspezies oder allgemeiner langlebige Übergangsmetallkomplexe, welche mit Radikalen reagieren, diskutiert – ein Gebiet, das jüngst stark expandiert ist.

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“…1c). We hypothesize that the direct utilization of the radical intermediate (B) with copper catalysis [47][48][49][50][51] by the merger of photocatalysis [52][53][54][55][56][57] to give desired ɤ-alkynylated carbonyl compounds. However, several highly competitive reactions have to be suppressed.…”

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confidence: 99%

Unified and practical access to ɤ-alkynylated carbonyl derivatives via streamlined assembly at room temperature

Shu

2019

Commun Chem

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The development of a unified and straightforward method for the synthesis of ɤ-alkynylated ketones, esters, and amides is an unmet challenge. Here we report a general and practical protocol to access ɤ-alkynylated esters, ketones, and amides with diverse substitution patterns enabled by dual-catalyzed spontaneous formation of C sp3-sp3 and C sp3-sp bond from alkenes at room temperature. This directing-group-free strategy is operationally simple, and allows for the straightforward introduction of an alkynyl group onto ɤ-position of carbonyl group along with the streamlined skeleton assembly, providing a unified protocol to synthesize various ɤ-alkynylated esters, acids, amides, ketones, and aldehydes, from readily available starting materials with excellent functional group compatibility.

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Rapid Synthesis of γ-Arylated Carbonyls Enabled by the Merge of Copper- and Photocatalytic Radical Relay Alkylarylation of Alkenes

Cited by 68 publications

References 60 publications

The Persistent Radical Effect in Organic Synthesis

The Persistent Radical Effect in Organic Synthesis

Der “Persistent Radical Effect” in der organischen Chemie

Unified and practical access to ɤ-alkynylated carbonyl derivatives via streamlined assembly at room temperature

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